Acylamines of the anthraquinone series and a process for their manufacture



Patented May 1, 1945 NI -S A E NT f OFFICE ACYLAMINES or 3 THE ANTHRAQUINONEI seams AND PROCESS FOR THEIR.

MANUFACTURE Albin Peter, Basel, Switzerland, assignor to Sandoz q A. G.,,Fribourg, Switzerland, a firm No Drawing.- Application January 16, 1942, Serial No;427,076. ,In Switzerland November 6, 1940 Claims. (01160 -276) The present inventionrelates to new acylainines of the antraquinone series which are valuable vat dyestuffs usefulfor dyeing different kinds of textiles and other materials and to a'. process for the manufacture of the new compounds.

I have found that newajcylamines of the anthaquinone series can be obtained by condensing such l-benzoylamino l-(carboxyl-phenylaminoanthraquinones that contain a substituted or unsubstituted carboxyl group with vattable derivatives of anthraquinones which contain at least i one primary amino group. i 1 The l benzoylamino-4-(carboxy) -phenylar'ninoanthraquinones that I use in the present process can contain substituentssuch as-halogen; cyano, alkyl, and ,acylamino, and the latter may be of aliphatic or of aromaticnature.

The starting products of the above cited configuration can be prepared in any known manner, 7

for example by condensation ofhalogenanthraquinones with aminobenzoic acid, or by condensation of aminoanthraquinones with halogenbenzoic acids-by splitting off the sulphonic acid, group from 1 aniinol-(carboxyphenyl) aminoanthra quinone-2-sulphonic acids which themselves can be obtained by condensation of l-amino-l-halogenantharquinone-2'-sulphonic acid with aminobenzoic acids and by subsequent acylation of the free amino group.

By vattable anthraquinone derivatives containing at least one primary amino'group I mean those derivatives of anthraquinone that can be transformed into leuco compounds. As such derivatives that I preferably use in order to carry out my invention I cite herein the following: aminoanthraquinones, such as land Z-aminoanthraquinone, 1-amino-3-bromoanthraquinone, 1-amino-5-, -6-, -'7- and 8-ch1oroanthraquinone, l amino-6,7-dichloranthraquinone, l-amino-4-,, -5- and -8--hydroxyanthraquinone, 1-amino-4- methoxyanthraquinone, 1,4-, 1,57, 1,8- and 2,6 diaminoanthraquinone, 1-amino-4-, -5- and B-benzoylaminoanthraquinone, l-amino-l -phenylamidone; aminodiand poly-anthrimides such as the monoand diamino 1,1 dianthrimides, the monoand diamino-1,2'-dianthrimides, aminoand diaminothrianthrimides, such as for example the 4-amino-1,1- and -1,2'dianthrimide, 5-amino-1,1-and 1,2"-dianthrimide, 4,4'-diamino-1,1'- dianthrimide, 4,5-diamino 1,1 dianthrimide, 5,5'-diamino 1,1 dianthrimide, 414a-diamino- 111z-5z13trianthrimide, as well as their halogenated derivatives, such as 5-amino-6'-chloro-1,1- dianthrimide, 4,4 diamino-6,6-dichlor-l,1'-dianthrimide, 4 amino-6'-chlor-1,2'-dianthrimide, 4-amino-6-chlor-L2-dianthrimide and so on.

The condensation to the new acylamines is carried out by heating the carboxy compound in a solvent such as chlorobenzene, dichlorobenzene,

trichlcrobenzene, nitrobenzene with phosphorus trichloride, phosphorus pentachloride, thionyl chloride, whereby the c arboxy compound becomes transformed into the carboxychloride derivative and-if desired;afterseparation of the acid chlonoanthraquinone, 1-amino-4-(2'-ch1orophenyl)-, f

-(3 chlorophenyl) -(4-chlorophenyl) aminoanthraquinone, l-ainino 4 (4'-methylpheny1) (4' methoxyphenyl) -=aminoanthraquinone, 1-

amino-4-pheny1amino-6- i or --7-chloranthraquinone and the derivatives which are substituted in the phenyl radical by halogen, alkyl and alkoxy; aminoanthrapyridones, such as 4-amino- N methyl 1(N) 9-anthrapyridone, 4-amino-N- methyl-C-acetyland --C-carbethoxyanthrapyridone, 4-amino-2-methyl-C-carbethoxy-; -C-carbomethoxy-, -C-benzoyl-, -C-acetyl -C-cyananthrapyridone, 5-amino-C-carboethoxy-l (N) 9-an thrapyridone; aminoanthrapyrimidines, such as 4 amino-1,9-anthrapyrimidine, 5-aminoanthrapyrimidine; amino anthraquinoneacridones, such as 4-aminoanthraquinone-lb (N) -benzacridone, 5- and 8-aminoanthraquinone-2,1-(N) -benzacriride and dissolving it in a fresh quantity of a solvent-40y heating it ,with a primary amine, if desired, in presence or acid binding compounds, suchas pyridine, dimethylaniline, alkaline metal acetates and the like.

The condensation can also be carried out by heating a mixture in a solvent such as chlorobenz ene, o-dichlorobenzene, trichlorobenzene, nitrobenzene in presence or absence of an acid binding agent, such aspyridine, dimethylaniline, alka limetal acetate, and in presence of a condensing compound, such as phosphorus pentoxide, sulphuric acids, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, zinc chloride, aluminium chloride, iron chloride, thionyl chloride and the like. In order to carry out the condensation I generally use the thionyl chloride because of its easy use.

The temperatures at which the condensation is carried out may vary in wide limits. Generally I heat the mixtures so long, until a test taken out and dissolved in alcohol shows that the quantity The new acylamines obtained by the present process are valuablevat dyestuffs yielding level dyeings of excellent stability to chlorine and to soda boiling. They can also be used as starting products for the preparation of other dyestufis.

The following examples, without being limitative, and the parts being by weight, illustrate the present process.

Example 1 10 parts of l benzoylamino 4-(4'-carboxy) phenylaminoanthraquinone are. treated during 1 hour at 120 C. with 4 partsof thionyl chloride in 100 parts of dry nitrobenzene. After distillin oif the excess of thionyl chloride in a dry air stream, 7.4 parts of 1-amino-5 benzoylamin'oanthraquinone are added to the solution and the whole is stirred during 1 hour'at 130-440 C. The condensation product which precipitates" is then filtered still warm and washed with nitrobenzene, ethanol and water. A dyestufi dyeing cotton fast olive shades from a dark blue -red vat is obtained. The new compound possesses" the for A similar dyestufi will be obtained when lbenzoylamino- 4(2"- carboxylphenylamioanthraquinone is used as acylating agent;

Example 2 the charge is stirred at 140*" C. until a test. taken out and dissolved in ethanol dyes the solvent only very pale. The reaction mixture is then diluted with ethanol at C. and. filtered. The new dyestuff dyes cotton grey shades, fast to bleaching from a dark blue-red vat and possesses the following formula:

Example 3 10 parts of l-benzoyhminoAMK-carboxy) phenylaminoanthraquinone are treated in parts of o-dichlorobenzene during 1 hour at C. with 5 parts of thionyl chloride. The excess of thionyl chloride is then distilled off and 2 arts of pyridine and 6.8 parts of 1-amino-4-phenylaminoanthraquinone are added to the charge, which is then stirred during 1 hour at -140 C. The dyestufi thus obtained is worked up in the same manner as described in Example 2 and is also identical with the dyestuff of this example.

Similar reddish to greenish-grey dyestuffs are obtained if instead of the phenyl derivative 1 amino 4- (2' chlorophenyl) -(3 chlorophenyl)-, -(4 chlorophenyl)'-, -(2' methylphenyl)--, -(3-methylphenyl)-, or -(4-methylphenyl) aminoanthraquinone is used.

I Ercample 4 8- parts of 1-benzoylamino-4(3-carboxy) phenylamino-anthraquinone, 5.4 parts of 1- amino-4- phenylaminoanthraquinone, 200 parts of o-dichlorobenzene and 10 parts of pyridine are stirred at 80 C. and treated with 3 parts of thionyl chloride. The temperature is then increased to C. and the charge stirred so long, until a test in alcohol shows no more change of the weak bluish shade. Then 0.5 part of thionyl chloride is'added thereto, stirred 1 hour longer and a test in alcohol is taken out again. This treatment is repeated until after a new addition of thionyl chloride no decrease of l-amino 4 phenylaminoanthraquinone can be found.

The new dyestufi is worked up in the'usual manner; it dyes cotton reddish-blue shades from a. dark blue-red vat and possesses the following formula:

By using l-amino-4-phenylamino 6 chloroanthraquinone instead of 1-amino-4-phenylaminoanthraquinone a dyestufi possessing a bluer shade will be obtained.

Example 5 I 7.9 parts.- of l-benzoylaminoA-(i'-carboxy)- Dhenylammoanthr'aquinone are heated under stirring with 3.9 parts of4,4 diamino-1,1'-dianthrimide. and 200parts of dichloro benzene. At 100 C. 3.2 parts of thionyl. chloride. are added thereto and thetemperature is increased up to C. After heating for 12 hours the reaction mixture is allowed to cool down; diluted with ethanol and theprecipitated dyestufifiltered. It dyes cotton Acylating agent Primary amine Color of the vet Dyeing 011' cotton 33 1-(2-chloro)-benzoy1amino-4-(3-carboxy-4- Diamino-anthra-rufine Dark-yellow-red... Violet.

chlorophenyl)-aminoanthraquinone. 34 do 4-am1no-N-methyl-anthrapyridone Dark-red BlQWIliSh-blflfikv10 35 l-benzoylaminoi-(4-carboxy) phenyl-aminol-aminoanthraquinone Dark-blue-red Olive.

an'thraquin'onc. 3 d 2-aminoanthraquinone Dark-yellow-red Greem'sh-grey.

1-amino-3-bromo-anthraquinon Dark-blue-red Grey.

l-amino-4-hydroxy-anthraquinon d Black-violet.

l-amino--methoxy-anthraquinone D0. 1,4-diamino-authraquinone. Reddish-grey. 1-amino-4-bcnzoylaminoanthra Black-violet. l-amino 4-phenyl-amino-anthraquinon Grey. 1amino-5-chloro-anthraquinone Reddish-grey. l-amino-fi-hydroxyanthraquinon Greenish-grey. 1,5-diamino-anthraquinone Black-brown. 1-amino-5-bcnzoylamino-anthr Olive. 1-amino-5-phenylamino-anthraquinone Reddish-grcy. l-amino-8-chl0ro-anthraquinone Black-olive.

1-(2', 4-dichloro) -benzoylamino4 (4-carboxy) phgnylaminoanthraquinone o 1-(2, 5-dichloroterephtha1oy1-)amino-4 (4- cagboxy)-phenylaminoanthraqumone. o

1 benzoylamino 4 (4' carboxy -2 methylphenyD-aminoanthraquinone.

1 lienzoylamino 4 (3 c'arbo'xy) phenyl aminoenthraquinone.

1 benzoylamino 4 (4 carboxy)-phenyl aninoanthraquinone V l-amino-B-hydroxyanthraquinone. LS-diaminoanthraquinone.

4-amino-anthraquinone-2, l-benzacridone 4-amino-N-methyI-anthrapyridone 4-amino-N-methy1-G-acetyl-anthrapyridone- 4-3mino-2-methyl- C -carbethoxy-anthrapyrione.

4-amino-anthra-pyrimidine 1-amino-4- (3-chloro)-pheny1-aminoanthraquinone. l-aminoi- (4-ch10ro)-phcny1-aminoanthraqu1- 4-amino-N-me thylanthrapytidone l-emino-4-methoxy-anthraquinone 1-amino4-pheny1aminoanthraquinone 1-amino-4-(4-ch1oro) phenylaminoanthraquinone. l-amino-fi, 7-dich1oro-anthraqumone 4-amino-N-methylanthraquinone 4-?1mino-2-methy1- C -carbethoxy-anthrapyrione. l-amino-4phenylaminoanthraquinone none. 1-amino-4-phenyl-a rninoanthraquinonc 4-amino-N-methyl-anthropyridonc 4-aminc-1, 1-dianthrim1de 4, 5-diamino-l, 1-dianthrimide 4-amino-l, 1'-dia nthrimide 4-amino-1, 2-dianthrimide.

5-amino-1, 1-dianthrimide D 5-amino-6-chloro-1,l-dianthrimide 5-amino-1, 2-dianthrimide 5, 5-diamino 1, 1'-dianthrimide Dark-blue-red.- do

Dark-red.

Dark-blue- Dark-rcd Dark-bluc-red...

,do Dark-red Dark-blue-rod.

Dark-red do -do Dark-b1ue-rcd do 'ii'r riiiijlijjl Dark-red-brown.

Dark-red Bordeaux-red Olive. Reddish-blackbrown. Blue-grey. Dark-brown.

. Do. Black-brown.

Olive. Reddish-grey.

Grey.

Reddish-grey.

Olive-grey.

Do. Grey.

Black-green.

Reddish grey.

Dark-brown. Reddish-blackbrown.

Grey.

Black-brown.

Dark-brown.

Grey.

Greenish-grey.

Black-brown. Dull violet.

Reddish-grcy.

Black-violet.

Do. Brown-violet. Reddish-grey.

Brown-vio1et.

What I claim is:

1. A process for the manufacture of dyestuffs or dyestufi. intermediates, comprising the step of condensing an anthraquinone compound of the general formula with a vattable anthraquinone compound containing at least one primary amino group, by heating the said compounds in the presence of an organic solvent comprising an acid acceptor.

2. A process for the manufacture of dyestuffs general formula or dyestuff intermediates, comprising the step of condensing an anthraquinone compound of the o NHOC 0 01 with a vattable anthraquinone compound containing at least one primary amino group, by heating the said compounds in the presence of an organic solvent comprising an acid acceptor.

3. A process for the manufacture of a dyestufi,

' comprising the step of heating the anthraquinone compound of the formula n NEG-Com with 4-aminoanthraquinone-2: 1 (N) -benzolacridone in the presence of an organic solvent comprising an acid acceptor.

4. A process for the manufacture of a dyestuff, comprising the step of heating the anthraquinone compound of the formula with l-aminoi-phenylaminoanthraquinone in the presence of an organic solvent comprising an acid acceptor.

5. A process for the manufacture of a dyestuff, comprising the step of heating the anthraquinone compound of the formula with 4:4'-diamino-1:1-dianthrimide in the presence of an organic solvent comprising an acid acceptor.

6. The compounds of the formula NH-O-c omrx wherein X represents the radical of a vattable anthraquinone compound, which compounds are vattable compounds possessing aflinity for fibers of cellulosic nature and which can be used as vat dyestuffs and as intermediate products for the manufacture or dyestuffs.

'7. The compounds of the formula is IIIH 0 1 a H O which is a vat dyestufi', dyeing cotton blue-grey shades from a dark-blue-red vat.

9. The compound of the formula which is a vat dyestuff, dyeing cotton grey shades from a dark-blue-red vat.

10. The compound of the formula NH-CO which is a. vat dyestufi, dyeing cotton level oliveblack shades from a dark-red vat.

ALBIN PETER. 

